DE2520430A1 - PROCESS FOR PRODUCING A CYCLOOLEFIN - Google Patents

Description

The invention "relates to a method of making a Cycloolefins by hydrogenation of an aromatic hydrocarbon .

It is known to produce cycloolefins by partial hydrogenation of the corresponding aromatic hydrocarbon in the presence of a ruthenium or rhodium-containing catalyst to manufacture. This method is known from the following publications ":

(1) U.S. Patent 3,391,206: hydrogenation in the presence of a lower alcohol;

(2) US Pat. No. 3,793,383: hydrogenation in the presence of an organic nitrogen compound;

(3) published Japanese patent application

No. 42645/1972: hydrogenation in the presence of water, Alkali and a reduced cation catalyst of at least one Group VIII element of the periodic table.

In processes (1) and (2), the selectivity and yield of cycloolefins are unsatisfactory. In the process (3) the reaction rate and the life of the catalyst are unsatisfactory.

509847/1161

It is therefore an object of the present invention to provide a process for the production of a cycloolefin from a hydrocarbon in high yield, "with a high reaction rate and a long service life of the catalyst used to accomplish.

According to the invention, this object is achieved by a process for producing a cycloolefin in which an aromatic Hydrocarbon of the formula

wherein R., R "and R, the same or different and are hydrogen atoms or G. - may represent C ^ alkyl groups, at 20-250 ⁰ C under a hydrogen pressure of 1 - is hydrogenated 200 atmospheres to give aqueous in an alkali-free medium in the presence of a carrier material loaded with Ru and / or Rh as a catalyst and in the presence of one or more metals from groups 1A and 2A of the periodic table and / or zinc and / or manganese and / or iron and / or the ions of these metals and / or ammonium works as a promoter.

As starting materials in the process of the present invention, aromatic hydrocarbons are as follows general formula used

509847/1161

2520A3Q

where R., Rp and R, can be identical or different and V / hydrogen atoms or C.sub.1 -C.sub.1 -alkyl groups. Suitable aromatic hydrocarbons are benzene, toluene, σ-, m-, p-xylene, ethylbenzene or the like.

The main components of the catalyst used are Ru and / or Rh. Ru and Rh can be used without a support material be used, e.g. B. in the form of ruthenium black and rhodium black. However, it is preferred to use a carrier material to be loaded with these catalyst components. Suitable carrier materials are zeolite, silicon oxide, kieselguhr, Sulicium oxide-aluminum oxide, aluminum oxide, titanium oxide or the like. The loading of a support material with Ru and / or Rh can conventionally by the immersion method, the concentration method, the drying method and the precipitation method be carried out using an aqueous solution of a ruthenium compound and / or a rhodium compound, e.g. B. the chlorides, nitrates, hydroxides, oxides or the like. Is used. The applied ruthenium compound and / or the rhodium compound is then made using a chemical reducing agent such as formalin or sodium borohydride or the like. Or reduced with the aid of hydrogen.

It is required the hydrogenation of the aromatic hydrocarbon to be carried out according to the present invention in an alkali-free aqueous medium. Furthermore, according to the invention worked in the presence of a promoter. This consists of one or more of the following components: Metals of groups 1A and 2A of the periodic table, zinc, manganese and iron, ions thereof and ammonium. As metals of groups 1A of the periodic table are preferred lithium, Suitable for sodium and potassium. The metals of group 2A of the periodic table are preferably magnesium, calcium, Strontium and barium are used. The promoter can be in the form of a cation in the aqueous medium. Further the carrier material loaded with Ru and / or Rh can also be loaded with the promoter. When the promoter is a cation

I 1 1

is present in the aqueous medium, this is preferably used in the form of a chloride or a sulfate. The amount of the promoter in the aqueous medium is usually in the range of 0.01-10 mol / l, and preferably 0.2-5 mol / l. If the catalyst is to be loaded with the promoter, the catalyst loaded with Ru and / or Rh is immersed in an aqueous solution of the promoter, preferably a chloride or a sulfate. The concentration of the promoter (salt) in the aqueous solution is not subject to any restrictions. However, it is usually in the range of 0.01% by weight to the saturation concentration at the temperature of the dipping treatment. The treatment with a promoter is preferably carried out at a temperature in the range from 20-250 ^° C. and in particular from 50-200 ^° C. and the duration of the treatment is preferably in the range from 10 min-10 h and in particular in the range from 1-5 h . The treatment is preferably carried out under a hydrogen atmosphere. If the promoter is applied to the support material before the support material is loaded with Ru and / or Rh, the life of the catalyst is considerably reduced. When the promoter is applied, the support material is treated in the same way as when the catalyst is produced. However, instead of hydrogen, one can work under an atmosphere of nitrogen or air. If the treatment is first carried out with a support material and Ru and / or Rh is applied and then the treatment is carried out with the product obtained, a catalyst with high activity and long life is obtained. In this treatment, the promoter is usually applied to the carrier material or the catalyst in an amount of 0.1-10% by weight, depending on the type of carrier material. If z. As a catalyst of 1 i ° Ru / siop in an aqueous solution of manganese chloride at 150 ⁰ C for 150 min under a water pressure of 40 atmospheres st off is immersed, so 1.20 wt .-% of manganese on the catalyst are applied . If the immersion time is 440 minutes under the same conditions, so

503847/1161

1.24 wt .- ^ manganese are applied. When SiO- is immersed for 120 minutes under the same conditions, 1.11 wt .- ^ manganese is deposited. When a catalyst of 1 $> Ru / LFA-Y-faujasite is immersed min at 90 ⁰ C for 180, so 6.4 wt .- ^ manganese are applied.

If the catalyst is treated with an aqueous solution of the promoter, it is not necessary to add a cationic promoter to the aqueous medium. The hydrogenation is thus carried out by contacting water, the aromatic hydrocarbon and hydrogen with the modified catalyst. The hydrogenation is thus carried out by contacting a mixture of water and the aromatic hydrocarbon and hydrogen with the catalyst. The hydrogenation of the aromatic hydrocarbon can be carried out in a fixed bed system or in a suspension bed system (fluidized bed system). The reaction temperature is usually in the range from room temperature to 250 ⁰ C and more particularly in the range 100-200 ⁰ C. The hydrogen pressure is usually in the range 1-200 atmospheres and preferably in the range of 5-100 atmospheres. The amount of the aqueous medium is usually in the range of 0.01-10, and preferably in the range of 0.05-5 in terms of the volume ratio of the aqueous medium to the aromatic hydrocarbon. It is necessary to use an aqueous medium which is alkali-free. In general, an aqueous medium of pH 2-7 is used. It is preferred to use water as the aqueous medium, which does contain the promoter but contains neither alkali nor acid. It is also preferred, when using the catalyst, to use water as the aqueous medium, which does not contain any additional agent.

In the following, the invention is explained in more detail with the aid of exemplary embodiments.

509847/1161

- D -

example 1

A 1 % Ru / Na faujasite catalyst is prepared in the following manner. Powdered Na-Y faujasite is dispersed in an aqueous solution of ruthenium chloride, and an aqueous solution of formalin is added dropwise to the mixture with stirring. An aqueous solution of sodium hydroxide is then added dropwise, ruthenium being deposited on the support material. The product is washed with water and dried at 100 ⁰ G, wherein the catalyst is obtained. 1 g of the catalyst, 30 ml of benzene, 20 ml of water and 3 g of sodium chloride are placed in a vertical 100 ml autoclave with a stirrer, whereupon the reaction is carried out at 150 ^° C. under a hydrogen pressure of 40 atmospheres.

Comparative example 1

The procedure of Example 1 is repeated, except that no sodium chloride is used.

Examples 2-9

The process according to Example 1 is repeated, using the salts given in Table 1 instead of sodium chloride can be used.

Comparative Examples 2-3

The process according to Comparative Example 1 is repeated, with the support materials according to Table 1 instead Na-Y-faujasite can be used.

Examples 10-11

The process according to Example 1 is repeated, except that the carrier material and the promoter according to Table 1 are different.

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_ ₇ _ 2520A30

place of Na-Y-faujasite and sodium chloride. Example 12

Powdered silicon oxide is formed into pellets which are loaded by the conventional dipping method with ruthenium chloride ". The mixture is stirred at 400 ⁰ C for 3 h calcined in air and then at 150 ⁰ C for 2 h reduced under a hydrogen gas flow, where 1 $ Ru / SiOp is obtained as a catalyst The process of the example is repeated using the catalyst obtained and manganese chloride as a promoter and using a shaking autoclave as the reaction vessel.

The organic liquid phase obtained in each case in Examples 1-12 and in Comparative Examples 1-3 is examined by gas chromatography. There will be a content of cyclohexene, cyclohexane and unreacted benzene
established. The results are shown in Table 1.

5 0 3 B A 7/1 1 6 1

Table 1

Promoter Reak
functional
duration
(min) Conversion
ment d.
Benzene Selectivi
for
Cyclohexene
(io) See-1 none 25th 60 6.7 Ex.1 NaCl 30th 60 15.0 Ex. 2 KCl 30th 60 16.0 Example 3 MgCl ₂ -6H ₂ O 30th 60 20.8 Ex. 4 CaCl ₂ -2H ₂ O 40 60 21.3 Ex. 5 ZnCl ₂ 200 60 24.2 Example 6 MnCl ₂ -4H ₂ O 30th 60 27.5 Ex. 7 MnSO ₄ -nH _{2 O} 30th 60 17.5 Example 8 NH.Cl 200 60 28.5 Ex. 9 (NH ₄ ) ₂ S0 ₄ 20th 55 19.3 See 2 none 40 50 3.3 Ex. 10 MgCl ₂ -OH ₂ O 200 75 10.7 See 3 none 25th 65 4.6 Example 11 MnCl ₂ • 4H ₂ O 30th 50 15.8 Example 12 Il 90 55 13.3 catalyst 1 io Ru / Na-Y-
Faujasite It Il Il Il Il Il Il Il Il 1 io Ru / SiO ₉ -
/ 1I ₂ O Il 1 io Ru / SiO ₂ It "(Pellets)

Example 13

A modified 5% Ru / Si0 ₂ ~ catalyst is produced as follows. A catalyst with the composition 5 ° Ru / SiOp is produced according to Example 1, silicon oxide being used instead of Na-Y-faujasite and sodium borohydride being used instead of formalin. Into the autoclave, 1.7 g of the catalyst, 3.0 g of manganese chloride and 20 ml of water and the mixture is treated h at 150 ⁰ C and a hydrogen pressure of 1 atmospheres while the second After cooling, the product is washed with water until no manganese chloride is found and then dried to give the modified catalyst. Pour into a vertical 100 ml stirred autoclave

b fj 3 8 4 7/1 1 B 1

1 g of the modified catalyst, 20 ml of water and 30 ml of benzene and then the reaction is carried out according to Example 1 carried out.

Comparative example 4

The process according to Example 13 is repeated, except that the catalyst is not treated with an aqueous solution of Manganese chloride is modified.

Example 14-20

The process according to Example 13 is repeated, using an aqueous solution of the respective salt according to Table 2 instead of the aqueous solution of manganese chloride is used, a modified catalyst is used in each case the composition 1 $ Ru / SiOp obtained.

Example 21

The process according to Example 13 is repeated, using a commercially available catalyst of the composition $ 2 treated with an aqueous solution of manganese chloride.

Comparative example 5

The process of Example 13 is repeated, using an unmodified commercial catalyst of the composition 25 & Rh / AlpO-z is used.

The results of Examples 13-21 and Comparative Examples 4-5 are shown in Table 2.

509847/1161

Table 2

catalyst Promoter Reak
functional
duration
(min) Conversion
ment of the
Benzene
(%) Selecti
vity for
Cyclo-
witches
(*) See 4 5% Ru / SiO ₂ no promoter 40 60 3.3 Ex. 13 Il MnCi ₂ -4H ₂ O 54 60 38.0 Ex. 14 1% Ru / SiO ₂ ZnCi ₂ 43 65 17.0 Ex. 15 η CaCi ₂ -2H ₂ O 44 65 17.0 Ex. 16 π FeCi ₂ ηΗ ₂ Ο 49 45 20.0 Ex. 17 π BaCi ₂ -2H ₂ O 47 60 13.0 Ex. 18 Il MgCi ₂ -6H ₂ O 34 70 19.0 Ex. 19 Il MnSÜ4-nH ₂ O 39 65 22.0 Ex. 20 Il NaBr 32 60 12.0 Ex. 21 2% Rh / Ai ₂ O ₃ MnCi ₂ .4H ₂ O 55 65 10.0 See 5 Il no promoter 16 60 1.7

Example 22

A catalyst 1% Ru / SiO is modified in the following manner ,,: In the autoclave are added 13 g silica, 7.5 g of manganese chloride and 50 ml of water and the mixture for 5 h "at 150 ⁰ C under an initial hydrogen pressure treated 30 atmospheres. After cooling, the carrier material is no longer manganese chloride is determined washed with water Ms and then at 100 ⁰ C dried. According to example 13 is then produced, a modified catalyst, except that the modified support material is used and wherein the formed Ru / SiO "catalyst is treated for 3 hours under an initial hydrogen pressure of 30 atmospheres in a solution of manganese chloride.

1 g of the modified catalyst, 20 ml of water and 30 ml of benzene are placed in a 100 ml vertical stirred autoclave and the reaction is carried out at 150 g under a hydrogen pressure of 40 atmospheres until a 60% conversion of the benzene is achieved. The time (θ.) For this reaction is 25 minutes. The reaction mixture is cooled and the entire organic liquid phase is removed from the autoclave and examined by gas chromatography. 30 ml of fresh benzene are placed in the autoclave, whereupon the reaction is carried out again under the same conditions until a benzene conversion of 60% is again reached. The same process is repeated. In the fifth repetition, the reaction time (θ [-) until a conversion of $ 60 is> 28 minutes. The results of the first to fifth conversions are summarized in Table 3. In addition, the results of Examples 23-38 below and Comparative Example 6 are shown in Table 3.

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Example 23

The procedure according to Example 22 is repeated, but where "at the carrier material is not modified with the salt.

Example 24

The process is repeated according to Example 22 -is, however, wherein the support material "is modified at 50 ⁰ C.

Example 25

The process according to Example 22 is repeated, but with the modification of the carrier material for 1 hour under a Nitrogen atmosphere at a pressure of 1 atm. instead of a hydrogen pressure of 30 atm. is carried out. Then the Catalyst modified with an aqueous solution of magnesium chloride instead of manganese chloride.

Examples 26-30

The process according to Example 22 is repeated, except that the support material and the catalyst loaded with Ru are also used an aqueous solution of the respective salt according to Table 3 can be modified.

Examples 31-35

The process according to Examples 26 to 30 is repeated, but with the carrier material prior to application of the Catalyst is not modified.

Example 36

Na-Y-faujasite is made with an aqueous solution of sodium chloride modified according to example 22 and Ru is applied according to example 1. The reaction v, -. Is five times under the

BG 3 8 k 7/1 1 B 1

The conditions of Example 1 were repeated using the same catalyst.

Comparison example 6

The procedure is repeated five times under the conditions of Example 1.

Example 57

The process according to Example 22 is repeated, T · aluminum oxide being used instead of silicon oxide as the support material and the support material being loaded with 2 ° rhodium instead of ruthenium.

Example 58

The process according to Example 57 is repeated, except that the carrier material is not modified.

509647/1161

Taoeile

Comment:

1) To the reaction system is added 3.0 g of sodium chloride ■ added.

22nd catalyst Promoter 4H ₂ O Treatment d.
Catalyst ZnCi ₂ 1st course Select.
f.Cyclo
hexeni *, 9 5th course Select
f.Cycl
witches ( I.
3 k V
3 23 % Ru / SiO ₂ Treatment d.
Carrier
i? erials MnCl ₂ - 4 H ₂ O FeCi ₂ . nH ₂ O min), 15th O -V
(min, 17th O. 89 E.g. 24 Il MnCi ₂ - 4H ₂ O Il BaCi ₂ -2H ₂ O »! 30th 8th 28 28. ο! O. 44 25th I! - Il MnSO ₄ • nH ₂ O 44 15th 4th OO 15th 8th O. 85 26th H MnCi ₂ ' 6H ₂ O MgCi ₂ -6H ₂ O MgCi ₂ . 6H ₂ O 25th 14th 7th 30th
j 14th ^7th O. 82 27 Il ti ZnCi ₂ I.
23 i 16. 1 28! 17th 4th O. 84 28 Il MgCi ₂ nH ₂ O FeCi ₂ ηΗ ₂ Ο 21 16. 8th 25th 15th 1 O. 88 29 It ZnCf ₂ 2H ₂ O BaCi ₂ -2H ₂ O 28 15th 5 32 16. O O. 79 30th Il FeCi ₂ - • nH ₂ O MnSO ₄ ■ nH ₂ O 30th 11 2 38 12th O O. 74 31 Il BaCi ₂ - - 26th 18th 3 35 18th 6th O 83 32 Il MnSO ₄ MnCi ₂ -4H ₂ O 20th 25th / 2 24 27 O O 67 33 Il - Il 40 17th .6 59 18th .8th O .47 34 Il - 39 18th .0 83 | 17th .4 O .56 '35 Il - 47 13th .4 84 12th .7 O .43 36 ¹
6 ¹ » Il - 43 24 .8th
.0 100 ! 23 .0
.6 O .48 37 1% Ru / Na-Y-
faujasite
Il - -4H ₂ O 40 14th
15th .6 84 ! 26
18th .8th O
O .86
.04 See. 35B 2% Rh / Ai ₂ O ₃ NaCi 30th
30th 9 .1 35
870 9 . 7th O
i .67 E.g. Il MnCi ₂ 32 11 48 11 O .31 E.g. - 50 160

cn K> O

IP -

Example 39

In a 100 ml autoclave 1 Priority g of the catalyst 1% Ru / Na-Y-type faujasite according to Example 1, 20 ml water, 30 ml of toluene and 3 g of manganese chloride and the reaction is "at 150 ⁰ C under a hydrogen gas pressure of 40 Atm The results are shown in Table 4.

Comparative example 7

The process according to Example 39 is repeated, except that no manganese chloride is used.

Example 40

According to Example 1 are added to the autoclave 1.7 g of the catalyst 1 $> Ru / Na-Y-Paujäsit, 20 ml of water and 0.1 g manganese chloride and the catalyst is at 120 ⁰ C for 30 min under a hydrogen gas pressure of 30 Atm. modified. The product is washed with water and dried to give a modified catalyst. 1 g of the modified catalyst, 20 ml of water and 30 ml of toluene are added to the autoclave and the reaction is carried out at 200 ^° C. under a hydrogen gas pressure of 60 atm. carried out until a toluene conversion of 60% is achieved. The implementation is repeated five times.

Example 41

The process according to Example 22 is repeated, using 0.5 g of manganese chloride instead of 7.5 g of manganese chloride will. Na-Y-faujasite is modified in the process. Under This modified support material is used as a catalyst of the 1 # Ru / Na-Y faujasite type according to Example 1 manufactured. This catalyst is further modified according to Example 40 and used for the hydrogenation reaction.

5 (1 ']'; ■■; 7/11 fi

Tabel

Reaction
"conditions 1. Procedure Reak
functional
duration
^θ 1
(min) Select.
for me
ethyl
cyclo
witches
OO 5. Procedure Selectivi
for
Methyl-
cyclohexene
(*) f See 7 150 ⁰ C
40 atm. Toluene-
umwand-
lung 50 4.0 Reak
functional
duration
⁹ 5
(min) Ex 39 It 50 110 30.0 40 200 ⁰ C
60 atm. 65 70 26.2 24.3 0.52 41 Il 60 55 22.8 135 22.0 0.85 60 65

Example 42

The process of Example 39 is repeated, using o-xylene instead of toluene. The reaction temperature is 180 ^° C.

Comparative example 8

The process according to Comparative Example 7 is repeated, using o-xylene instead of toluene, and using the reaction at a reaction temperature of 180 to be led.

¹ C through

Example 43

The process according to Example 40 is repeated using o-xylene instead of toluene.

Table 5

Reaction
conditions Conversion
ment of the
o-xylene
W. Selek
tivi
activity
OQ Reaction
duration
(min) See 8
Ex. 42
Ex. 43 180 ⁰ C
40 atm.
It
200 ⁰ C
60 atm. 55
60
35 5.3
35.0
29.0 100.
240
60

'' 1 6 1

Claims (1)

PATENT TO PROPOSALS (1. Process for the preparation of a cycloolefin by Hydrogenation of an aromatic hydrocarbon of the formula wherein R _1, R "and R, are the same or different and are hydrogen atoms or CL - C, alkyl" may mean at 20-250 ⁰ C under a hydrogen pressure of 1 - 200 atm in the presence of an aqueous, preferably alkali-free. Medium, characterized in that one (1) as a catalyst one charged with Ru and / or Rh Carrier material uses as well (2) as a promoter at least one of the metals of groups 1A and 2A of the periodic table and / or zinc and / or manganese and / or iron and / or ions of these metals and / or ammonium. 2. The method according to claim 1, characterized in that the promoter is used as a cation in an aqueous medium dissolves. 3. The method according to any one of claims 1 or 2, characterized in that one with the promoter tor loaded carrier materials. 4c method according to any one of claims 1 to 3, characterized characterizedj that one uses the promoter as ale chloride. 5c The method according to any one of claims 1 Ms A ₉ is germinated in that manganese chloride is used as a promoter Ο G 3 O h I ι \ 6. The method according to claim 2, characterized in that there is a concentration of the promoter in the aqueous Select medium from 0.01-10 moles / l. 7. The method according to any one of claims 1 "to 6, thereby characterized in that the carrier material used is zeolite, silicon oxide, silicon oxide-aluminum oxide, aluminum oxide or diatomaceous earth used. 8. The method according to any one of claims 3 "to 7, characterized characterized in that one uses a catalyst impregnated with the promoter, which is obtained by immersing the catalyst in an aqueous solution of the promoter. 9. The method according to any one of claims 3 to 7, characterized in that one impregnated with the promoter tor Catalyst is used, which by immersing the support material in an aqueous solution of the promoter, through the following Applying Ru and / or Rh to the treated carrier material and then immersing the obtained product was prepared in an aqueous solution of the promoter. 10. The method according to any one of claims 1 to 9, characterized in that the hydrogenation is carried out at ^{100-200 0} C under a hydrogen pressure of 5-100 atm. performs. 11. The method according to claim 10, characterized in that a catalyst is used, which by application of Ru and / or Rh on a support material and immersing the product obtained in an aqueous solution of at least one of the cations of sodium, potassium, magnesium, calcium, barium, zinc, manganese or Iron was made. 5 0 9 8 A 7/1 1 B 1 12. The method according to claim 10, characterized in that a catalyst is used, which by immersion a carrier material in an aqueous solution of at least one cation of sodium, potassium, magnesium, des Calcium, barium, zinc, manganese or iron and by subsequent application of Ru and / or Rh and by subsequently immersing the product obtained in an aqueous solution of at least one cation of sodium, potassium, magnesium, calcium, des Barium, zinc, manganese or iron. 13. The method according to any one of claims 11 or 12, characterized in that a catalyst is used in 'its preparation loaded with Ru and / or Rh support material at 50 to 200 ⁰ C was immersed under a hydrogen atmosphere in the aqueous solution. 14. The method according to any one of claims 11 to 13, characterized characterized in that a catalyst is used in the preparation of which a carrier material loaded with Ru and / or Rh is used was immersed in an aqueous solution of manganese chloride. 15. The method according to any one of claims 1 to 14, characterized characterized in that the aromatic hydrocarbon used is benzene, toluene or xylene. 16. The method according to any one of claims 1 to 15, characterized in that a volume ratio of the aqueous medium to the aromatic hydrocarbon from 0.01 - 10. 509847/1161